CN1176031C - Waste water treatment process and treatment appts. - Google Patents

Waste water treatment process and treatment appts. Download PDF

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CN1176031C
CN1176031C CNB021027870A CN02102787A CN1176031C CN 1176031 C CN1176031 C CN 1176031C CN B021027870 A CNB021027870 A CN B021027870A CN 02102787 A CN02102787 A CN 02102787A CN 1176031 C CN1176031 C CN 1176031C
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gas
mentioned
waste water
gasification
wastewater treatment
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CN1369444A (en
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�村淳志
岡村淳志
夫
佐野邦夫
明
池田光明
次
北浦正次
松島薰
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Abstract

Cleaning method and apparatus that are capable of treating both TMAH and ammonia at the same time while ammonia treatment method or a TMAH treatment method are conventionally known respectively. The method for cleaning wastewater [A] containing TMAH and ammonia [B] consists of an ammonia diffusion process (diffusion part 26) for diffusing ammonia in wastewater, a concentration process (concentration part 14) for concentrating wastewater after the diffusion of ammonia to obtain a high boiling point organic compound-containing concentrated liquid, a gasifying process (gasifying part 16) for gasifying the concentrated liquid and a decomposition process (decomposition part 18) for decomposing the gas obtained in the gasifying process and the diffused ammonia-containing gas using a catalyst.

Description

Wastewater treatment method and treatment unit
Technical field
The present invention relates to a kind of wastewater treatment method and treatment unit, described treatment process and treatment unit are to the waste water that contains gasifiable organic compound and contain and can carry out method and the treatment unit that the waste water of the compound (to call the compound that annoying handling goes out in the following text) that gas carries is handled simultaneously with gas.The present invention relates to a kind of waste water that gasifiable organic compound and annoying handling go out compound that just contains again, and wherein organic compound and annoying handling gone out the method and apparatus that compound is handled simultaneously.Though below, be to be example about above-mentioned gasifiable organic compound with tetraalkylphosphoniuhydroxide hydroxide amine, going out compound about annoying handling again is in addition mainly explanation of example with ammonia, process object of the present invention is not limited to above-mentioned ammonia and tetraalkylphosphoniuhydroxide hydroxide amine.
Background technology
Annoying handling goes out the typical example of compound can enumerate ammonia, and the method for ammonia is catalyst treatment method and biological treatment in the known existing processing waste water.
Above-mentioned catalyst treatment method at first is that ammonia gas from waste water is carried, and ammonia is contacted and oxidation with catalyzer, resolves into harmless nitrogen G﹠W.(opening flat 7-289897 communique) as the spy
Above-mentioned biological treatment is to utilize action of microorganisms, the ammonia in the waste water is become the method for nitrogen G﹠W.But the processing efficiency of biological treatment is low, obtain the amplification that processing power efficiently need depend on unit scale, and owing to produced excess sludge, also has the problem of handling these mud.
As the material that the need that contain in the waste water are discharged, have and to put forward essence with gas gas and emit, but can make all gasifiable organic compound of gasification of waste water again.This organic compound is an example with tetraalkylphosphoniuhydroxide hydroxide amine.As the facture of the waste water of the organic compound that contains tetraalkylphosphoniuhydroxide hydroxide amine and so on, known have burning method, microorganism treatment, a supercritical water disaggregating treatment method.
Above-mentioned burning method is that waste water is at high temperature burnt, and makes the oxidized disaggregating treatment of the organic compounds containing nitrogen that contains in the waste water.At this moment, the organic compound (organic compounds containing nitrogen) that usually contains nitrogen from the such molecule of above-mentioned tetraalkylphosphoniuhydroxide hydroxide amine for example can generate oxynitride (NOx).Because must be equipped with the treatment facility that makes this NOx become more harmless material, so burning method exists equipment enlarging, shortcoming that construction cost is high.
The mentioned microorganism method is by microbial process, makes the organic compounds containing nitrogen disaggregating treatment become the method for harmless nitrogen, water, carbonic acid gas etc.This microorganism treatment is the same with above-mentioned burning method, and processing efficiency is low, and treatment facility must maximize, and also must consider the handling problem of excess sludge.
The disaggregating treatment method of above-mentioned use supercritical water is to utilize the physics of supercritical state water and the method for chemical property.Water just can be in supercritical state under the high temperature and high pressure state because must be controlled at, so thermotolerance, resistance to pressure to treatment unit have strict requirement, and obtain high pressure, equipment such as high-pressure pump, high pressure compressor must be arranged, so equipment costs a lot of money.
The inventor is for solving the problem about the purifying treatment of tetraalkylphosphoniuhydroxide hydroxide amine etc., just organic compounds containing nitrogens such as above-mentioned tetraalkylphosphoniuhydroxide hydroxide amine are become the innocuous gas that nitrogen, carbonic acid gas etc. do not need aftertreatment, discharge method for waste water, propose new motion, and applied for patent (patent No. 2000-114086).
Summary of the invention
As mentioned above, with regard to the method that tetraalkylphosphoniuhydroxide hydroxide amine etc. and ammonia are handled respectively, existing people has proposed scheme, but also not to containing the method that the two waste water is handled simultaneously.And because semiconductor device manufacturing works and various chemical plant discharge various waste water, if kind and processed material at processed waste water adopt various treatment unit, then have and be necessary for the very big place of treatment facility preparation and need the very high cost of equipment and the problem of operating cost.
The object of the present invention is to provide a kind of method of wastewater treatment and treatment unit, described method and apparatus can be handled different types of waste water simultaneously, promptly handle simultaneously with the waste water of ammonia etc. containing tetraalkylphosphoniuhydroxide hydroxide amine etc., thus, make treatment process and the treatment unit that wastewater treatment equipment is simple, the equipment input is cheap.
From the waste liquid that representative is arranged of discharges such as semiconductor device manufacturing works is the waste water (to call waste water [B] in the following text) that contains the compound that annoying handlings such as ammonia go out, the waste water (to call waste water [A] in the following text) that contains organic compound such as hydroxide tetraalkyl amine, and, to contain the waste water of organic compound such as ammonia and tetraalkylphosphoniuhydroxide hydroxide amine.The inventor finds: if with ammonia and tetraalkylphosphoniuhydroxide hydroxide amine (to call TMAH in the following text) as the process object material in the waste water, then for decomposition product and the ammonia of thermal degradation TMAH, in order to titanium dioxide and silica composite oxide is support of the catalyst, contains the catalyzer (TiO of vanadium, tungsten, palladium 2SiO 2VW Pd) after same catalyzer is done catalytic treatment, can discharge nitrogen (N 2), oxygen (O 2), water (H 2O), carbonic acid gas (CO 2).
And the present inventor finds: catalyzer is if use above-mentioned TiO 2SiO 2V W Pd catalyzer then is not limited to the resultant of the above-mentioned TMAH of thermolysis, also can handle the organic compound of 2-pyrrolidone, monoethanolamine, ethylene glycol and so on, and the annoying handling that can handle beyond the ammonia goes out compound (as amine, tetrahydrofuran (THF)).The present inventor further finds, also exists other many energy disaggregating treatment such as above-mentioned organic compound and annoying handling to go out the catalyzer of compound, thereby finishes the present invention.
The method of wastewater treatment of relevant the 1st invention of the present invention is a kind of method of wastewater treatment that can handle two or more waste water simultaneously, the a kind of of above-mentioned waste water is the waste water [A] that contains gasifiable organic compound, the another kind of above-mentioned waste water is to contain the waste water [B] that can carry out the compound that gas carries with gas, its main points are that aforesaid method comprises: the gasification process of above-mentioned waste water [A] that gasify; From above-mentioned waste water [B], gas is put on and is stated and can put forward operation with the gas that gas carries out the compound that gas carries; The gas (to call [A] gasifying gas in the following text) that will obtain by above-mentioned gasification process, and carry gas (going out gas) that operation obtains by above-mentioned gas and mix (group) and lump together, pass through the decomposition process that catalyzer carries out disaggregating treatment to call the handling of [B] gas in the following text.
As realizing as the treatment unit of the treatment process of the 1st invention of the present invention is a kind of wastewater treatment equipment that can handle two or more waste water simultaneously, the a kind of of above-mentioned waste water is the waste water [A] that contains gasifiable organic compound, the another kind of above-mentioned waste water is to contain the waste water [B] that can carry out the compound that gas carries with gas, its main points are that said apparatus comprises: the gasification portion of the above-mentioned waste water [A] that gasifies; From above-mentioned waste water [B], gas is put on and is stated and can carry portion with the gas that gas carries out the compound that gas carries; The gas (to call [A] gasifying gas in the following text) that will obtain by above-mentioned gasification process, carry the gas (going out gas) that obtains by above-mentioned gas and mix, carry out the decomposition portion of disaggregating treatment through catalyzer to call the handling of [B] gas in the following text.
As above, make two or more waste water become the gas shape,, after above-mentioned catalyst decomposes processing, various waste water are handled respectively these waste water also together, can simplify treatment facility, reduce process cost.
In addition, above-mentioned " gas is carried " is to be dissolved in volatile component in the liquid (to call the dissolving volatile component in the following text) with the operation that gas is discharged from, gas at this moment is the gas that does not contain above-mentioned dissolving volatile component, and the gas handling goes out this gas by contact afterwards with solution.Such operation is carried in gas.Go out operation by such gas handling, the gas handling that contains volatile component goes out gas and separates with the liquid phase that volatile component reduces.Above-mentioned " gasification " is by the method to liquid enforcement heating or decompression etc., and whole liquid is evaporated, and is gasiform operation, and thus, the feasible composition that is dissolved in the liquid is evaporated with all liquid or gasifies.In a word, " gas is carried " is with gas volatile component to be discharged from liquid, discharges the operation of volatile component in the liquid that reduces, and by contrast, " gasification " is all operations of liquid evaporation and aerification.
Above-mentioned gasifiable organic compound is example with boiling point at the organic compound below 800 ℃, and the compound handled of suitable the present invention be boiling point more than 100 ℃, the organic compounds containing nitrogen below 600 ℃.What be more suitable for is that boiling point is more than 100 ℃, the organic compounds containing nitrogen below 350 ℃.
Above-mentioned gasification process (gasification portion) is, as (1): and waste water is sprayed to the space of heating, waste water is all gasified, or (2): by heated waste water, the operation of evaporation and gasification waste water.The concrete enforcement of the gasification process of above-mentioned (1) is as follows, at normal pressure, more than 100 ℃, is preferably, and more than 250 ℃, is preferably in more than 500 ℃, waste water is sprayed at the space of heating.Like this, to high temperature, the waste water of spraying is evaporated by heating space, and the organic compound that contains in the waste water is also gasified simultaneously.In addition, even contain the macromolecular organic compound of difficult evaporation, more than 500 ℃ the time, also can be decomposed and gasify.The tetraalkylphosphoniuhydroxide hydroxide amine that contains in the waste water of the etched plate of semiconductor device manufacturing is broken down into Trimethylamine 99 and methyl alcohol at 130 ℃, is gasified simultaneously.
In addition, the treatment process of relevant the 1st invention of the present invention preferably before above-mentioned gasification process, concentrates the enrichment process of above-mentioned waste water [A].Again, in the treatment unit of relevant the 1st invention of the present invention, be preferably in before the above-mentioned gasification of the importing portion, the concentrated portion that concentrates above-mentioned waste water [A] is set.Concentrated portion can adopt well-known methods such as method of evaporation, freezing freezing method, membrane separation process.
By above-mentioned enrichment process (concentrate portion) waste water [A] is concentrated in advance, can reduce next operation gasification process (gasification portion) gasification the heat that must provide.
In addition, about the treatment process of the 2nd invention of the present invention is that a kind of processing contains gasifiable organic compound and can carry out the method for wastewater treatment of the waste water of the compound (compound that annoying handling goes out) that gas carries with gas, its main points are that this treatment process comprises: above-mentioned annoying handling goes out compound and puies forward operation from the gas that the handling of liquid phase gas goes out; Concentrate the enrichment process of above-mentioned gasifiable organic compound; The gasification process of the concentrated solution that the gasification enrichment process obtains; To obtain gas and carry the decomposition process that gas that operation obtains decomposes in the presence of catalyzer in gasification process at above-mentioned gas.
Handle the wastewater treatment equipment that contains gasifiable organic compound and can carry out the waste water of the compound (compound that annoying handling goes out) that gas carries with gas about the treatment unit system of the waste water of the 2nd invention of the present invention.Its main points are that this treatment unit comprises: above-mentioned annoying handling goes out compound and carries portion from the gas that the handling of liquid phase gas goes out; Concentrate the concentrated portion of above-mentioned gasifiable organic compound; The gasification portion of the concentrated solution that the gasification enrichment process obtains; Will be in the decomposition portion that gasification portion expellant gas and the gas that obtains in the above-mentioned gas portion of carrying decompose in the presence of catalyzer.
In addition, be meant, be dissolved in volatile component in the solution (to call the dissolving volatile component in the following text), do not contain the gas that dissolves volatile component and contact with solution and gone out by the gas handling with the operation that gas is discharged from as above-mentioned " gas is carried ".And above-mentioned " gasification " is to be evaporated and to gasify by composition of liquid being implemented the method for heating or decompression, made whole liquid be evaporated the operation that is gaseous phase, make to be dissolved in the solution and all liquid.
As above-mentioned, is example with the high boiling point organic compound of boiling point below 800 ℃ as above-mentioned gasifiable organic compound, relatively is suitable for compound that the present invention handles and is boiling point more than 100 ℃, organic compounds containing nitrogen below 600 ℃.What be suitable for handling most is boiling point organic compounds containing nitrogen below 350 ℃ more than 100 ℃.Concrete example is an example with the hydroxide alkylamine, and the example that representative is arranged especially is tetraalkylphosphoniuhydroxide hydroxide amine (TMAH).Again, as annoying handling go out compound with ammonia as representative.When making, semiconductor device discharges the waste water that contains above-mentioned TMAH and ammonia.
All gasify if contain the waste water of TMAH and ammonia, after the gas of gasification was handled by catalyst decomposes, gasification installation necessarily required to maximize, and also will increase with the amount of the increase catalyzer of gas volume, and what the device that catalytic decomposition is handled also will be very is big.In addition, be warmed up to the temperature that makes the gas that imports catalyticreactor and reach the temperature that reaction is fit to, very many heats must be arranged.
As the present invention, if go out the waste water of compound from the annoying handling of the gasifiable organic compound that contains TMAH etc. and ammonia etc., extract gases such as spissated TMAH and spissated ammonia, the size that the size of gasification installation (gasification portion) will reach degree such as gasifiable concentrated TMAH at least gets final product, be that smaller degree gets final product, and the power consumption of gasification installation (gasification portion) is lacked when gasifying not concentrated solution.In addition, reduce, can use less decomposer (decomposition portion) owing to import the gas volume of decomposition process.Therefore, whole just seem very terse of treatment unit.The feasible required necessary heat of design temperature that is warmed up to the catalyticreactor of decomposition process (decomposition portion) reduces significantly.And, from operating cost and initial investment, be very economic treatment process and device.
The method and apparatus of the 2nd invention of the present invention is not limited only to contain the processing of the waste water of ammonia and TMAH, also is applicable to as the waste water that contains ammonia and 2-pyrrolidone etc., contains the processing of the waste water of gasifiable organic compound beyond the TMAH and ammonia.And be applicable to the waste water that contains compound (as amine, tetrahydrofuran (THF)) that the annoying handling beyond the ammonia goes out and TMAH etc.Be that the present invention a kind ofly uses said structure to containing the method that waste water that annoying handlings such as gasifiable organic compound such as TMAH and ammonia go out compound carries out purifying treatment, can be simultaneously, efficiently TMAH etc. and ammonia etc. are processed into nitrogen (N 2), carbon dioxide (CO 2), water (H 2O) etc.
Above-mentioned gasification process (gasification portion) in the method (device) of the 2nd invention of the present invention is the operation of whole concentrated solutions gasifications that will obtain from above-mentioned enrichment process.[1] only concentrated solution is imported gasification portion (gasification process) and gasify, or [2] imports under the state of gasification portion (gasification process) gas being carried the gas (containing ammonia gas etc.) that portion's (gas is put forward operation) obtains, provide above-mentioned concentrated solution to gasify.Perhaps, also can import under the state of gasification portion (gasification process), provide above-mentioned concentrated solution to gasify at the gas after the processing will discharging from [3] decomposition portion (decomposition process).In a word, can gasify to concentrated solution by various ways.
And for example above-mentioned [2], as the gasification treatment device in the time will importing the state of gasification portion, can enumerate and have the treatment unit that the gas that above-mentioned gas is carried portion imports the pipeline of above-mentioned gasification portion and the discharge concentrated solution of above-mentioned concentrated portion imported the pipeline of above-mentioned gasification portion from the gas that gas is carried portion.
Gas that above-mentioned gasification process (gasification portion) can be obtained and above-mentioned gas handling go out gas and handle at decomposition process (decomposition portion) respectively, but after gas that above-mentioned gasification process is obtained and above-mentioned gas are carried gas that operation obtains and are mixed, the method of carrying out decomposition process again can be more efficient, and can simplification device.When being tetraalkylphosphoniuhydroxide hydroxide amine, preferably isolating tetraalkylphosphoniuhydroxide hydroxide amine and ammonia are mixed once more, decompose at decomposition process as above-mentioned organic compound, promptly the decomposition gas of tetraalkylphosphoniuhydroxide hydroxide amine and ammonia are mixed, carry out catalytic decomposition, the simplification of then its efficient height, and device.
The treatment unit of the 2nd invention of the present invention has: the gas that 1. imports gasification portion is not only above-mentioned concentrated solution (containing liquid such as TMAH), also import the gas that obtains in the gas portion of carrying, the mixed gas of the TMAH decomposition gas that gasification portion is discharged etc. and ammonia etc. imports the occasion of above-mentioned decomposition portion in addition, 2. gasification portion only imports above-mentioned concentrated solution, in the gas of TMAH decomposition gas that gasification portion discharges etc., mix ammonia etc., it is imported the occasion of above-mentioned decomposition portion, 3. gasification portion only imports above-mentioned concentrated solution, and the gases such as TMAH decomposition gas that gasification portion is discharged are gentle puies forward the occasion that portion's expellant gas imports each self-decomposition portion respectively.Wherein, above-mentioned as 1., refining plant 2. is simple and efficient.
The above-mentioned gasification process of the 2nd invention of the present invention (gasification portion) is the same with above-mentioned the 1st invention, can enumerate as (1): above-mentioned concentrated solution is sprayed in the space of heating, makes the operation of whole waste water gasifications, or (2): heated waste water, make it evaporation, the operation of gasification.
Further, the treatment process of relevant the 2nd invention of the present invention, preferably above-mentioned gas is put forward operation and is carried out before above-mentioned enrichment process, and the liquid phase after gas is carried just invests above-mentioned enrichment process.
This gas is put forward the situation (putting forward type in advance to call gas in the following text) that operation is carried out earlier than above-mentioned enrichment process, put forward the situation (to call the type in advance that concentrates in the following text) that operation is carried out earlier compared with enrichment process described later than gas, addition that reduces alkali and the advantage of utilizing treating water are easily again arranged.
Gas is carried the refining plant of type in advance and can be enumerated by above-mentioned waste water being imported above-mentioned gas and carry the pipeline of portion and the discharge liquid phase that gas is carried portion is imported the device that the pipeline of above-mentioned concentrated portion is formed.By such device, waste water is carried portion through gas earlier, handles in concentrated portion again.
Or the purification method for effluent of relevant the 2nd invention of the present invention, be preferably, above-mentioned enrichment process adopts the spissated operation of heat energy, making above-mentioned enrichment process put forward operation than above-mentioned gas carries out earlier, the gas phase that enrichment process is obtained is brought into the condensation operation, and the water of condensation that obtains is brought into above-mentioned gas and carries in the operation.
As, utilize water vapor to heat above-mentioned waste water, obtain the liquid phase portion (enrichment process) that ammonia etc. is volatilized and be concentrated, evaporable ammonia etc. be condensed simultaneously with water vapor (condensation operation), subsequently, the ammonia in the water of condensation etc. is gone out (gas is put forward operation) by the gas handling, on the other hand, the concentrated solution that contains organic compound that above-mentioned enrichment process obtains is gasified (gasification process), and gas that this gasification process obtains and above-mentioned gas are put forward the gas catalyst decomposes (decomposition process) that operation obtains.
So, also can carry out gas and put forward operation prior to enrichment process.
As concentrating the refining plant of type in advance, can enumerate by the heating unit of the pipeline that above-mentioned waste water is imported above-mentioned concentrated portion, the above-mentioned concentrated portion of heating, the gas phase of will the portion of concentrating discharging import the condensation part pipeline, the discharge condensed water of condensation part imported gas carry the device that the pipeline of portion is formed.By this device, at first through concentrating portion, the gas phase that concentrates portion is condensed in the condensation part waste water, and the water of condensation of discharge is handled in the gas portion of carrying, and contains the gas (as containing ammonia gas) that annoying handling goes out compound and is gone out by the gas handling.
In addition, the treatment process of relevant the 1st, 2 invention of the present invention preferably is used the maintenance heat that above-mentioned gas is carried the gas after the processing of operation as the gasification heat in the above-mentioned gasification process.
Carrying the gas extracting method of operation can enumerate as gas, 1.: by the heated waste water (waste water that contains TMAH etc. and ammonia, or waste water [B]), carry out the method that the gas handling goes out, 2.: will contain the gas (as air) of oxygen and/or steam and import air-lift device (gas is carried portion, makes annoying handling such as ammonia go out method that compound is discharged from above-mentioned oxygen containing gas and steam etc.But go out gas through [B] gas handling that above-mentioned gas extracting method 1. obtains, contain the gas that annoying handling goes out compound, and in above-mentioned gas extracting method 2., [B] gas handling of using above-mentioned steam to carry out obtaining when the gas handling goes out goes out gas and contains the gas that annoying handling goes out compound, all is in than under the higher temperature.Again, in above-mentioned gas extracting method 2.,, also be still containing the method efficient height that oxygen-containing gas (as 100～200 ℃) than comparatively high temps imports air-lift device even carry out gas when carrying with oxygenous gas, so the oxygen-containing gas that heating imports is general method.Therefore in any situation, put forward operation (gas is carried portion) through gas and obtain the handling of [B] gas and go out gas, contain the gas that annoying handling goes out compound and all be in than under the higher temperature.
Thereby,, can be reduced to the required heat energy cost of gasification by in above-mentioned gasification process (gasification portion), effectively utilizing going out gas than [B] gas handling of higher temperature like this and containing the maintenance heat that annoying handling goes out the gas of compound.
Again, gasification heat as above-mentioned gasification process, ([B] gas handling of first invention of the present invention goes out gas also can to utilize the gas that obtains of the above-mentioned gasification process of heating, or the gas handling of second invention of the present invention goes out gas), make to keep heat further to improve (heating process (heating part)), with the thermal source of its utilization as gasification process.
As the heating means of heating process, can make well-known methods such as electrical appliance heating and roasting kiln.The fuel of above-mentioned roasting kiln, certainly use kerosene, liquefied gas (LPG) and piped gas etc., because the waste liquid that contains Virahol of semiconductor device manufacturing works and solvent slop are discharged from from clean operation etc. sometimes, if effectively utilize above-mentioned waste liquid and solvent slop fuel as roasting kiln, from reducing viewpoint of energy, be ideal.
Again, the catalytic treatment of decomposition process is carried out after generally will heat up (as 250～350 ℃), utilizes above-mentioned heating process, and heating [B] gas handling goes out more than the temperature that gas (the gas handling that annoying handling goes out compound goes out gas) sets to above-mentioned catalytic treatment.Like this, utilize the handling of [B] gas to go out the heat of gas (the gas handling that annoying handling goes out compound goes out gas) as the needed high temperature of above-mentioned gasification process, then, continue to import decomposition process, then need not be used for the well heater of the decomposition process of catalyzer, thereby make device simple, efficient improves.
Again, in the treatment process of relevant the 1st, 2 invention of the present invention, the maintenance heat that preferably is used to the gas (exhaust) after the processing of above-mentioned decomposition process is as the required heat of above-mentioned gasification process gasification.And in the relevant treatment unit of the 1st, 2 invention of the present invention, the maintenance heat that preferably is used to the gas (exhaust) after the processing of above-mentioned decomposition portion is as the required heat of above-mentioned gasification portion's gasification.
When handling with catalyzer in the decomposition process (decomposition portion), from the viewpoint of the processing efficiency of catalyzer, preferably the temperature with processed gas is elevated to the temperature (as 250-350 ℃) that sets.Thereby, in decomposition portion, can or heat the reactor that is filled with catalyzer, or the gas of heating imported reactor.So, the gas temperature height of decomposition process, thereby the exhaust of coming out from decomposition process (decomposition portion) also has than higher temperature.Therefore.As utilize deflated to keep heat in above-mentioned gasification process (gasification portion), and then can effectively utilize heat, reduce the power consumption cost that is used to gasify.
As the method for utilizing of the heat of the gas after handling, can enumerate as by heat exchange, heat is transferred to the handling of [B] gas from the gas of above-mentioned processing go out the gas (or contain the gas handling that annoying handling goes out compound go out gas).
As device, can enumerate a circulation line that above-mentioned decomposition portion expellant gas is turned back to above-mentioned gasification portion is set.
Also can will further heat, further improve maintenance heat (heating process (heating part)), can utilize the thermal source of above-mentioned exhaust as above-mentioned gasification process (gasification portion) from the exhaust of thermal degradation operation (decomposition portion).For example, can enumerate the circulation line that the discharge gas from above-mentioned decomposition portion is turned back to above-mentioned gasification portion through the heating part.During the above-mentioned shortage of heat that is used to gasify, available heating part boosting.The heating means of this heating process (heating part) are with above-mentioned the same, and with well-known methods such as electrically heated, roasting kilns, the fuel of above-mentioned roasting kiln can be used kerosene, liquefied gas (LPG), piped gas etc.And preferably effectively utilizing the waste liquid that contains Virahol (solvent slop) of the discharges such as clean operation of semiconductor device manufacturing, as the fuel of above-mentioned roasting kiln, if utilize waste liquid like this, from the angle that energy reduces, is desired.
In the treatment process of the 1st, 2 invention of the present invention, be preferably, the waste water after carrying gas that operation obtains via above-mentioned gas and carrying is carried out harmless treatment.
Because contain various objectionable constituent in the waste water after gas is put forward sometimes, preferably carry out harmless treatment as above.Above-mentioned harmless treatment can be enumerated such as using catalyst-free oxide treatment operation and catalytic treatment operation, and biologic treatment process etc. are carried out harmless treatment thus.
Again, the above-mentioned waste water [B] in the 1st invention of the present invention is when containing hydrogen peroxide, and after hydrogen peroxide was put forward operation through above-mentioned gas, in the waste water after being contained in gas and carrying, after handling through the solid catalyst of gac etc., hydrogen peroxide can be broken down into harmless water (H 2O) and oxygen (O 2).
Again, as above-mentioned gasifiable organic compound, if water-soluble material, then its kind is not particularly limited, following compound is arranged specifically: urea, hydrazine, pyridine, piperidines, pyrazine, pyrazoles, pyrazoline, 2-pyrrolidone, the N-vinyl pyrrolidone, also just like the alkyl quaternary amine salt of tetraalkylphosphoniuhydroxide hydroxide amine and hydroxide tetraethyl-amine, choline etc., alkanol amine as monoethanolamine, diethanolamine etc., as the organic acid of formic acid, acetate, vinylformic acid etc., as decompose after the thermolysiss such as amine acetate, ammonium formate gasification organic acid amine salt class.Wherein, particularly the waste water that contains tetraalkylphosphoniuhydroxide hydroxide amine of semiconductor device manufacturing works discharge is maximum, so it is the most effective to handle this waste water the present invention.
Again, the above-mentioned annoying compound of carrying, if water-soluble material, and have with gas or steams such as air or with gas and the steam materials that the gas handling goes out from waste water such as air, then the kind of compound is not particularly limited.Specifically be exemplified below: ammonia, ethylenemine ether, THF or as alcohols such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, as aldehydes such as formaldehyde, acetaldehyde, as ketones such as 2-acetone, 2-butanone, hydrazine classes such as N-N dimethylhydrazine are as amines such as methylamine, ethylamine, dimethyl amine, Trimethylamine, triethylamines.Wherein, particularly the waste water that contains ammonia of semiconductor device manufacturing works discharge is maximum with the waste water that contains ammonia and hydrogen peroxide, so it is the most effective to handle this waste water the present invention.
Again, as the catalyzer that is used for above-mentioned decomposition process (decomposition portion), as long as the compound that above-mentioned gasifiable organic compound and above-mentioned annoying handling are gone out decomposes available multiple catalyzer simultaneously.As, except above-mentioned TiO 2SiO 2Outside the VW Pd catalyzer, other catalyzer, as precious metals such as platinum, palladium, rhodium, iridium, ruthenium, silver, or as transition metal such as copper, manganese, nickel, cobalt, chromium, caesium, iron, all can be supported at oxide compound as the catalyzer on the carrier (oxide carriers such as silicon-dioxide, aluminum oxide, titanium dioxide, zirconium dioxide, cerium oxide) alone or in combination as activeconstituents.Other can be enumerated with lanthanum, caesium, strontium, platinum, manganese, nickel, cobalt, copper, iron etc. as the composite reactive composition, are supported at above-mentioned lanthanum etc. as the catalyzer on the above-mentioned oxide matrix.
At above-mentioned organic compound is that tetraalkylphosphoniuhydroxide hydroxide amine, described gasifiable compound are the occasion of ammonia, used catalyzer can enumerate with comprise titanium dioxide and/oxide compound of titanium dioxide and silicon-dioxide is as first composition; The oxide compound that is selected from least a metal in palladium, tungsten, molybdenum, caesium and the iron is as second composition; Be selected from least a metal from platinum, palladium, iridium, manganese, rhodium, ruthenium, chromium and copper or its oxide compound catalyzer as the third composition.
Description of drawings
Fig. 1 is the wastewater treatment equipment mode chart of the relevant embodiment of the invention 1.
Fig. 2 is the wastewater treatment equipment mode chart of the relevant embodiment of the invention 2.
Fig. 3 is the wastewater treatment equipment mode chart of the relevant embodiment of the invention 3.
Fig. 4 is the treatment unit mode chart of the relevant embodiment of the invention 4.
Fig. 5 is the treatment unit mode chart of the relevant embodiment of the invention 5.
Fig. 6 is the treatment unit mode chart of the relevant embodiment of the invention 6.
Fig. 7 is the treatment unit mode chart of the relevant embodiment of the invention 7.
Among the figure, 11,21 is jar, 12,22 are waste water importing pipeline, 13,23 is the wastewater discharge pipe road, 14 is thickener, 15 is the concentrated solution escape route, 16 is gasifier, and 17 is the gas outlet pipe road, and 18 is hydrogen-catalyst reactor, 19,39 for handling gas outlet pipe road, back (handling vent pipes such as back gas), 20 is fuel supply pipe, and 24 is the PH regulating tank, and 25 enter pipeline for waste water, 25a, 28a, 31a is a pump, 26 is gas stripping column, and 27 is the alkali groove, and 28 is the alkali supply pipe, 29,45 is the gas outlet pipe road, 31 are liquid discharge tube road (liquid discharge tube (wastewater discharge pipe that does not contain NH3)), and 32 for steam imports pipeline, and 33 is the air leading-in conduit road, the 33a air fan, 34,35,37,56,58,65,83 is well heater, and 36 is circulation line, and 36a is a fan, 38 send pipeline for waste water, 41,42 is branch line, 43,44 is heat exchanger, 46,47 is discharge pipe, 48 for merging pipeline, 55,68 is air leading-in conduit, and 61 are steam importing pipe arrangement, 62,72 are waste water importing pipe arrangement, 63 are the supply pipe arrangement, 64 is gas outlet pipe, and 66 is thickener, and 67 are concentrated solution discharge pipe arrangement, 69 are vaporize water derivation pipe arrangement, 70 is vent pipe, and 71 is the gasifying gas vent pipe, and 73 is gas outlet pipe, 74 is the steam supply pipe, 75 are phlegma discharge pipe arrangement, and 76 are the heating thickener, and 77 is liquid discharge tube, 78 is the condensation part, and 81 for dividing branch road.87 is that heat exchanger is used in gasification, and 89 are the air heating heat exchanger.
Embodiment
Below, with reference to exemplifying accompanying drawing, add a concrete explanation with regard to treatment process of the present invention and treatment unit, among the present invention, be not limited to following cited example, other implementation methods can be made suitable change in the suitable scope of the present invention's design, but no matter do which kind of change, all are included in the technical scope of the present invention.
Embodiment 1
Fig. 1 is the wastewater treatment equipment mode chart of relevant embodiments of the invention 1.
Jar 11 is jars of the temporary transient above-mentioned waste water of storage [A], jar 11 connection waste water importing pipeline 12 and wastewater discharge pipe roads 13.Wastewater discharge pipe road 13 is connected with thickener (concentrating portion) 14, and the concentrated solution escape route 15 of deriving from thickener 14 is connected with gasifier (gasification portion) 16.
Jar 21 is jars of the temporary transient above-mentioned waste water of storage [B], and jar 21 imports pipeline 22 with waste water and is connected with wastewater discharge pipe road 23.Wastewater discharge pipe road 23 is connected with pH regulator groove 24, and in the pH regulator groove 24, alkali groove (alkali lye holding tank) 27 is connected with confession alkali pipeline 28 by being exclusively used in the pump 28a of alkali.The waste water of deriving from above-mentioned pH regulator groove 24 drops into pipeline 25, by dropping into pump 25a, is connected with gas stripping column (gas is carried portion) 26.
The following quadrate part of gas stripping column 26 is connected with the steam that imports steam and imports pipeline 32 and import the air leading-in conduit road 33 that adds warm air.In the air leading-in conduit road 33 of above-mentioned importing air air fan 33a is installed.In the above-mentioned air leading-in conduit road 33, import air outside by well heater 34.The upper portion of gas stripping column 26 is connected with the escape route 29 of discharging internal gas, and on the other hand, gas stripping column 26 bottoms are connected with the liquid discharge tube road 31 of the liquid in the vent gas stripper 26.Be provided with pump 31a in this liquid discharge tube road 31, expel liquid is imported next operation.
Above-mentioned gas escape route 29 is connected with above-mentioned gasifier 16 by well heater 35.The gas outlet pipe road 17 that connects gasifier 16 is connected with hydrogen-catalyst reactor (decomposition portion) 18, is provided with from this hydrogen-catalyst reactor 18 and handles gas outlet pipe road, back 19.As the catalyzer of above-mentioned hydrogen-catalyst reactor 18, be filled with the oxide compound that comprises titanium dioxide and/or titanium dioxide and silicon-dioxide as first composition; The oxide compound that is selected from least a metal in palladium, tungsten, molybdenum, caesium and the iron is as second composition; Be selected from least a metal in platinum, palladium, iridium, manganese, rhodium, ruthenium, chromium and the copper or its oxide compound catalyzer as the third composition.
Below just be illustrated with the method for wastewater treatment of the treatment unit of embodiment 1.
Above-mentioned waste water [A] is example with the waste water of the circuit card that semiconductor device manufacturing process discharges, and contains the organic compound of TMAH and so in this waste water.Above-mentioned waste water [B] can exemplify the ultrasonic clean waste water of semi-conductor, contains ammonia and hydrogen peroxide in this waste water.
At first, the above-mentioned waste water [B] of discharging from jar 21 is imported pH adjust groove 24, add alkali.So, nationality improves the ammonia of gas stripping column 26 and puies forward efficient by waste water is made alkalize.Can use many alkali as above-mentioned alkali, get final product so long as can make aqueous solution be alkalescence.For example, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide etc. are arranged.The alkali number that adds in the waste water, as long as the ammonia handling is gone out, with any amount can, the amount of alkali is controlled at the pH value that makes waste water gets final product greater than 7.Be preferably, alkali number is controlled at and makes the pH value reach 7-13.Alkali number makes the pH of waste water less than 7 o'clock, and the gas handling of ammonia goes out efficient and will reduce, and on the other hand, if pH is 13 when above, the alkali number of interpolation will be too much, causes the expense raising.
Then, the waste water [B] that adds alkali is imported gas stripping column 26.At this moment, import through the air (as 100-200 ℃) of the heating on air leading-in conduit road 33 and/or through steam and import the steam of pipeline 32, ammonia that contains in the above-mentioned waste water [B] and above-mentioned air etc. together, as ammoniated gas, 29 discharge from the gas outlet pipe road.Like this, the ammonia of above-mentioned waste water [B] is proposed separation (gas is put forward operation) in gas phase side by gas.
The operational condition of gas stripping column 26 is preferably in below 120 ℃, below the pressure 20kPa (gauge pressure), according to being used in the gas that the gas handling goes out, can do following classification.That is, when going out with gas handlings such as air and nitrogen, preferably temperature is at 5-50 ℃, and pressure (gauge pressure) below 20kPa is operated; When carrying with steam gas, best operational condition be temperature at 80-120 ℃, pressure is below 20kPa (gauge pressure).Again, the gas input amount of using when the gas handling goes out, when going out with gas handlings such as air and nitrogen, the volume ratio of waste water input amount is preferably 100-10000 times relatively, and 1000-5000 is doubly better.When going out with the handling of steam gas, preferably 0.05-10 times of relative waste water input amount, weight ratio, 0.1-5 is doubly better.
Remove the waste water (below, be called the waste water of deammoniation) of deammoniation in the above-mentioned gas stripping column 26,31 flow out from the liquid discharge tube road, again through as the solid catalyst processing, disaggregating treatment hydrogen peroxide etc.
Then, above-mentioned gas escape route 29 is discharged contains ammonia gas, is heated to 200-600 ℃ (best more than 500 ℃) by well heater 35, imports gasifier 16.
On the other hand, the waste water in the jar 11 [A] T is imported thickener 14.Approximately contain the TMAH of 2000ppm as the circuit card waste water of discharging from semiconductor device manufacturing process, if low like this concentration, the gasification of following gasifier 16 need consume too much heat, and efficient is very low.Thereby, as above-mentioned, in the thickener 14 that sets in advance, gas concentration is arrived the concentration of setting.Through concentrating, can obtain roughly not containing organic water.This water can be used as the service water recycle, and extraordinary effect is arranged.
Then, concentrated solution is sprayed in the above-mentioned gasifier 16, utilizes the above-mentioned heated heat that contains ammonia gas, make above-mentioned concentrated solution gasified (gasification process).And TMAH is being broken down into methyl alcohol and Trimethylamine 99 (below, claim TMA) and is being gasified more than 130 ℃.
Then, the gas (gas that contains ammonia, methyl alcohol, Trimethylamine 99) that comes out from gasifier 16 imports hydrogen-catalyst reactor 18, and the catalyst decomposes in reactor 18 is handled, and becomes CO 2, O 2, H 2Innocuous gas such as O (decomposition process) are discharged from escape route 19.
The temperature that imports the gas of hydrogen-catalyst reactor 18 is preferably in 100-400 ℃.Carry out catalysis less than 100 ℃, then oxidation efficiency is insufficient, may also have above-mentioned ammonia etc., and on the other hand, if temperature surpasses 400 ℃, above-mentioned ammonia etc. can further oxidation, generates oxynitride (NOx) easily, also must consider the aftertreatment of NOx.Therefore, said temperature is preferably in more than 250 ℃, below 350 ℃.And preferably the catalysis space velocity (SV) of hydrogen-catalyst reactor 18 is with 500～5000h -1(1000-10000h -1Better) offer above-mentioned processed gas.As this speed less than 500 -1, it is very big that reactor 18 must be done, and efficient is very low, and surpasses 50000h -1The time, decomposition efficiency may significantly reduce.
Again, preferably, remove not vaporized solid matter, only gaseous constituent is imported in the reactor 18 by above-mentioned gasifier 16.That is, in waste water to be processed, except that organic compounds containing nitrogen, hydrocarbon polymer, also contain containing metal element (for example Si) and sulphur and also be difficult to the organic compound (rubber and heat-curing resin etc.) that decomposes in gasification process.These materials, were preferably removed them before from gasification process to the catalyzed oxidation operation because gasification process can't make it gasification from gas.These compositions that are difficult to gasify are the objectionable impuritiess that make poisoning of catalyst, also are the reasons that causes the reaction efficiency reduction of catalyzed oxidation operation.Remove harmful toxic matter, the most handy pretreating reagent is removed.Described pretreating reagent the most handyly is selected from least a in aluminum oxide, silicon-dioxide, titanium dioxide and the zirconium dioxide.These pretreating reagents form particle shape usually and use, but do not limit especially.
So, can handle simultaneously two kinds of waste water that contain waste water [A] and waste water [B].
Embodiment 2
Fig. 2 is the mode chart of the wastewater treatment equipment of relevant embodiments of the invention 2.With the same component part of Fig. 1 with same symbolic representation, avoid repeat specification.
The treatment unit system of present embodiment 2 utilizes from the heat of the innoxious gas of hydrogen-catalyst reactor 18 discharges, the device that gasifies in gasifier 16.Gas after the processing,, is connected with gasifier 16 through well heater 37 by fan 36a through ramose circulation line 36 from escape route 19.Be connected from the escape route 29 of gas stripping column 26 pass-outs and the gas outlet pipe road 17 of gasifier 16.In present embodiment 2, omitted above-mentioned thickener 14, the wastewater discharge pipe road 38 of jar 11 directly is connected with gasifier 16.Other structures are the same with the foregoing description 1.
The same with the foregoing description 1, the ammonia in the waste water [B] is gone out by the gas handling, obtains ammoniated gas.
On the other hand, waste water [A] is sprayed at gasifier 16[A] in gasify.At this moment,, be heated to the necessary temperature of gasification,, import above-mentioned gasifier 16 and be used for gasification as 200-600 ℃ by well heater 37 through the innoxious gas of escape route 19 from ramose circulation line 36.Because of the temperature of the innoxious gas of the discharge of above-mentioned escape route 19 just in time is fit to the temperature of catalyzer, as 100-400 ℃ high temperature, therefore, utilize these heats, can reduce the heat that adds of well heater 37, good thermo-efficiency is arranged.
Then, from gasifier 16 expellant gas with from the gas mixing that contains ammonia that above-mentioned gas escape route 29 is discharged, import catalyticreactor 18.The same with the foregoing description 1, through catalyst action, being decomposed is treated to N 2, CO 2, O 2, H 2Innoxious gas such as O is discharged from escape route 19.
Like this, can handle two kinds of waste water that contain waste water [A] and waste water [B] simultaneously.
Embodiment 3
Fig. 3 is the mode chart of the wastewater treatment equipment of relevant embodiments of the invention 3.With the same component part of Fig. 1 with same symbolic representation, avoid repeat specification.
In present embodiment 3, the escape route 39 of gas has two branches after the processing of deriving from hydrogen-catalyst reactor 18, and a branch line 41 and gasifying is connected with heat exchanger 43, and another branch line 42 is connected with heat exchanger 44 with air heating.
Above-mentioned gasification is with being connected with the gas outlet pipe road 45 of deriving from gas stripping column 26 on the heat exchanger 43, by heat exchange, but the gas that contains ammonia in the heated air escape route 45.In heat of gasification interchanger 43, the heating part is set again, can be heated to and makes waste water [A] the necessary temperature (200-600 ℃) that gasifies.Use the escape route 45 of heat exchanger 43 to be connected through aerifying, be used for the gasification of waste water [A] with gasifier 16.
On the other hand, above-mentioned air heating is with being connected with the air leading-in conduit road 33 that is used for air is imported gas stripping column 26 on the heat exchanger 44, can heat air in the air leading-in conduit road 33 by heat exchange.Again, air heating can be heated to suitable temperature with in the heat exchanger 44 heating part being set.Adopt air heating to be imported into gas stripping column 26 with the air of heat exchanger 44 heating through air leading-in conduit road 33, the gas handling that is used for ammonia goes out.
Innoxious gas process escape route 46,47 is mixed in the pipeline 48 of interflow after the heat exchange, is discharged in the atmosphere.
As above-mentioned,, therefore,, can effectively utilize heat if use above-mentioned heat exchanger 43,44 to recycle heat because the innoxious gas of discharging from hydrogen-catalyst reactor 18 is in than higher temperature.
Present embodiment 3 can be handled two kinds of waste water of waste water [A] and waste water [B], its thermo-efficiency height simultaneously also with above-mentioned the same.
Embodiment 4
Fig. 4 is the mode chart of the treatment unit of relevant embodiments of the invention 4.The upper portion of gas stripping column (ammonia is carried portion) 26 is connected with the importing pipe arrangement (importing pipeline) 62 that imports the waste water that contains ammonia and TMAH, and gas stripping column 26 inside have the structure that above-mentioned waste water is injected from top to bottom.At the upper section of gas stripping column 26, installed again internal gas expellant gas vent pipe 64.The following quadrate part of gas stripping column 26 is equipped with the supply pipe arrangement 63 of supply air or steam, and the bottom of gas stripping column 26 is equipped with the liquid discharge tube (liquid discharge tube road) 31 that the liquid in the gas stripping column 26 is discharged.This liquid discharge tube road 31 is connected with thickener (concentrating portion) 66, has again, and the concentrated solution derivation pipe arrangement 67 of deriving from thickener 66 is connected with gasifier (gasification portion) 16.Also be connected with on the above-mentioned thickener 66 and discharge the pipe arrangement 69 that concentrates the distilled water that generates, and be connected with the steam importing pipe arrangement 61 that is used to heat this concentrated portion 66.
The gas outlet pipe 64 that connects from above-mentioned gas stripping column 26 is connected with well heater (heating part) 65.And in gas outlet pipe 64, be connected with air leading-in conduit 68, the ammoniated gas (NH that obtains at gas stripping column 26 3Gas) add an amount of air in, be supplied to well heater 65.Connect fuel supply pipe 20 on the above-mentioned well heater 65, with the ammoniated gas of heating from gas outlet pipe 64 importings.The ammonia gas that contains that is heated to design temperature at above-mentioned well heater 65 is supplied to gasifier 16 by vent pipe 70.Gasifier 16 is derived pipe arrangement 67 with above-mentioned concentrated solution and is connected, and above-mentioned concentrated solution is sprayed in the ammoniated gas that above-mentioned well heater 65 has been heated to certain temperature, and concentrated solution is all gasified.
The vent pipe 71 that is connected with above-mentioned gasifier 16 is connected to hydrogen-catalyst reactor (decomposition portion) 18, by above-mentioned gasifier 16, above-mentioned concentrated solution can being gasified, (thermolysis concentrates the TMAH that contains to the discharge gas that generates, generate Trimethylamine 99 and methyl alcohol etc.), with by gas outlet pipe 64, after the ammoniated gas that process well heater 65 imports gasifiers 16 is mixed into mixed gas, import hydrogen-catalyst reactor 18.
Be provided with the vent pipe (handling gas outlet pipe road, back) 19 of discharging the gas after handling in the hydrogen-catalyst reactor 18.And can suitably regulate air import volume from 68 li of the air leading-in conduits that is connected with above-mentioned gas vent pipe 64, like this, can be with the concentration adjustment of the ammonia in the gas that imports in the above-mentioned hydrogen-catalyst reactor 18 and above-mentioned Trimethylamine 99, methyl alcohol to the concentration that is suitable for the catalyzed reaction in the hydrogen-catalyst reactor 18.
Be filled with catalyzer in the above-mentioned hydrogen-catalyst reactor 18.The catalyzer of filling in the hydrogen-catalyst reactor 18 preferably contains, as, the oxide compound that contains silicon-dioxide and/or silicon-dioxide is as composition A; The metal oxide of choosing any one kind of them at least from vanadium, tungsten, molybdenum, caesium and iron is as composition B; The oxide compound of metal from platinum, palladium, iridium, rhodium, ruthenium, manganese, chromium and copper, choose any one kind of them at least as composition C.
Fortune work to the treatment unit of embodiment 4 is illustrated below.
The waste water that will contain TMAH and ammonia imports the gas stripping column 26 from pipe arrangement 62.At this moment, import air or steams from supply pipe arrangement 63, the ammonia that contains in the above-mentioned waste water becomes ammoniated gas with above-mentioned air etc., discharges from gas outlet pipe 64.So, ammonia gas from above-mentioned waste water is carried and be separated to gas phase side.
The operational condition of gas stripping column 26 is preferably, and temperature is below 120 ℃, and pressure is (gauge pressure) below 20kPa, and the gas that uses when handling goes out according to gas can be classified as follows.
When [1] carrying out the gas handling and go out with air and nitrogen etc., best operational condition is temperature 5-50 ℃, pressure 20kPa (gauge pressure); When [2] carrying out the gas handling and go out with steam, best operational condition is temperature 80-120 ℃, below the pressure 20kPa (gauge pressure).Again, the amount that the gas that the gas handling go out to be used drops into, when [1] is carried out the gas handling and is gone out with air and nitrogen, the input amount of waste water relatively, volume ratio preferably 100-10000 doubly, more than 1000 times, below 5000 times better.When [2] carrying out the gas handling and go out with steam, the input amount of waste water relatively, weight ratio preferably 0.05-10 doubly, more than 0.1 times, better below 5 times.
Then, the waste water after the ammonia handling gone out (below, claim to remove NH 3Waste water) discharge from the liquid discharge tube 31 of gas stripping column 26, import thickener 66.Thickener 66 imports the steam-heated cal(l)andria that pipe arrangement 61 imports, the then above-mentioned NH that removes as using from steam 3Waste water in moisture be evaporated (vaporize water is discharged pipe arrangement 69 from vaporize water and discharged), obtain the concentrated solution of TMAH.The water of evaporation is distilled water, behind the cooling condensation, and the recyclable service water etc. that is used further to.
From above-mentioned gas vent pipe 64 with above-mentioned ammoniated gas through certain air dilution (mixing the air of coming in) back importing well heater 65 time from air leading-in conduit 68, from fuel feed pipe 20 fuelings, make by fuel burner, produce 200-600 ℃ hot blast.When the ammoniated gas of heating is imported into gasifier 16 through vent pipe 70, with the concentrated solution of above-mentioned TMAH from pipe arrangement 67 to gasifier 16 internal sprayings, above-mentioned TMAH concentrated solution is gasified.TMAH is broken down into methyl alcohol and Trimethylamine 99 (below be sometimes referred to as TMA), gasification through the high temperature more than 130 ℃.Heating means as gasifier 16 are not limited to above-mentioned fuel burner again, also available electrically heated.
Then, will import hydrogen-catalyst reactor 18, be decomposed the N of generation by the catalyst action in the hydrogen-catalyst reactor 18 from above-mentioned gasifier 16 expellant gas (gas that contains ammonia, methyl alcohol, Trimethylamine 99) 2, CO 2, H2O discharges from vent pipe 19.The temperature of hydrogen-catalyst reactor 18 preferably is controlled at 100-400 ℃ (being more preferably 250-350 ℃), and this temperature is less than 100 ℃, and then catalyst oxidation efficient is not high, probably also has residues such as above-mentioned ammonia.On the other hand, said temperature surpasses 400 ℃, and then ammonia etc. is generated oxynitride (NOx) easily by undue oxidation, and must consider the aftertreatment of NOx this moment.The catalysis space velocity (SV) of hydrogen-catalyst reactor 18 is 500-50000h preferably -1(1000-10000h -1Better) offer above-mentioned processed gas, less than 500h -1It is big that hydrogen-catalyst reactor 18 must be done, and efficient is very low, surpasses 5000h -1Then decomposition efficiency obviously reduces.And in addition, be preferably in and remove not vaporized solid matter in the above-mentioned gasifier 16, and only gaseous constituent is imported in the hydrogen-catalyst reactor 18.
So, can be simultaneously, efficiently the wastewater treatment that contains TMAH and ammonia is become harmless N 2, CO 2, H 2O.Directly the waste water that contains TMAH and ammonia is gasified, when using catalyst treatment, aforesaid large-scale plant must be arranged, but in case TMAH is separated with ammonia, regasify behind the TMAH of concentrating and separating, with above-mentioned isolating ammonia through catalyst treatment, treatment unit Miniaturizable then.
Embodiment 5
Fig. 5 is the mode chart of the wastewater treatment equipment of relevant embodiments of the invention 5.With the same component part of Fig. 4 with same symbolic representation, to avoid repeat specification.
The pipe arrangement 72 that conveying contains TMAH and ammonia is connected with thickener (concentrating portion) 76, and thickener 76 is connected with steam supply pipe 74, utilizes the steam-heated cal(l)andria of this pipe supply.Be connected with gas outlet pipe 73, liquid discharge tube 77 from thickener 76, this liquid discharge tube 77 is connected with gasifier (gasification portion) 16.Again, above-mentioned gas vent pipe 73 is connected with condenser (condensation part) 78, and condenser 78 is connected to gas stripping column (ammonia is carried portion) 26 by pipe arrangement 75.Part is equipped with the supply pipe arrangement 63 of air or steam below gas stripping column 26, and the bottom of gas stripping column 26 is equipped with the vent pipe 31 that the liquid (water after the processing) in the gas stripping column 26 is discharged.Again, the gas outlet pipe 79 that connects from gas stripping column 26 links to each other with gasifier 16.Be connected with the pipe arrangement 57 of deriving on the above-mentioned vent pipe 79 from well heater (heating part) 56.Be connected with fuel supply pipe 20 and air leading-in conduit 55 on this well heater 56.The vent pipe 71 that connects autopneumatolysis device 16 is the same with the foregoing description 4, is connected with hydrogen-catalyst reactor 18, and the vent pipe 19 of gas after the processing that ejects autocatalysis agent reactor 18 is installed.
Work to the device of present embodiment 5 is illustrated below.
At first, the waste water that contains ammonia and TMAH is imported thickener 76, in this thickener 76, waste water is by steam-heated cal(l)andria, and TMAH is concentrated.In 76 evaporations of this thickener, the main component of 73 expellant gas is water vapour and ammonia from gas from vent pipe.Then in condenser 78 condensations, water of condensation enters gas stripping column 26 through pipe arrangement 75.At gas stripping column 26, by air or steam the ammonia handling in the water of condensation is gone out, the gas that contains the ammonia that the gas handling goes out from gas outlet pipe 79 discharge and heater via 56 heated air mixed after, import gasifier 16.
On the other hand, the TMAH concentrated solution that obtains at above-mentioned thickener 76 imports above-mentioned gasifier 16.The TMAH concentrated solution is gasified in gasifier 16, discharges from vent pipe 71 simultaneously with the gas that contains above-mentioned ammonia, imports hydrogen-catalyst reactor 18.The gas that imports TMA and methyl alcohol that to be ammonia and nationality generated by the decomposition of TMAH, these gases are decomposed simultaneously, purify through the Decomposition of the catalyzer of hydrogen-catalyst reactor 18, discharge N from vent pipe 19 2, CO 2, H 2O (innoxious gas).
So, can be simultaneously, efficiently the wastewater treatment of two kinds of materials that contain TMAH and ammonia is become harmless N 2, CO 2, H 2O.
As the heating means of thickener 76, in present embodiment 5, exemplified steam-heated cal(l)andria, but be not limited thereto, well-known methods such as available electrically heated, roasting kiln.The fuel of above-mentioned roasting kiln also can be used kerosene, liquefied gas (LPG), piped gas, contains the waste liquid of Virahol and the solvent slop discharges such as matting of semiconductor device manufacturing works (often from) etc. in addition.
Embodiment 6
Fig. 6 is the mode chart of the refining plant of relevant embodiments of the invention 6.With the same component part of Fig. 4 with same symbolic representation, to avoid repeat specification.
The refining plant system of the embodiment of the invention 6 utilizes from the heat of the innoxious gas of hydrogen-catalyst reactor 18 discharges, alleviates the burden of well heater., is connected and the mixing of ammoniated gas by blower fan 82 from vent pipe 19 ramose branched bottoms 81 with gas outlet pipe 64 from gas stripping column 26.Form the circulation line 80 that is back to gasifier 16 from vent pipe 19 thus.Other structure is the same with the foregoing description 4.
The same with the foregoing description 4, ammonia carries out gas at gas stripping column 26 to be carried, and obtains ammoniated gas (NH 3Gas).Do not contain NH from what gas stripping column 26 was discharged 3Waste water in thickener 66, concentrate, concentrated solution imports above-mentioned gasifier 16.Above-mentioned ammoniated gas is by circulation line 80, utilizes the maintenance heat of supply gas and heats up, again 83 temperature (as 200-600 ℃) that are warmed up to setting in the heating part.Be expelled to the temperature of the innoxious gas in the vent pipe 19, because of exothermic catalytic reaction, temperature than the gas that imports hydrogen-catalyst reactor 18 taller (the suitable temperature of catalyzed reaction such as 100-400 ℃), so utilize these heats, the heat that adds of well heater (heating part) 83 can be suppressed, reduces, its thermo-efficiency height can reduce the energy consumption that is used to gasify.
Then, be imported into the hydrogen-catalyst reactor 18 from gasifier 16 expellant gas, the same with the foregoing description 4, through the catalyst action disaggregating treatment, generate N 2, CO 2, O 2, H 2Innoxious gas such as O is discharged from vent pipe 19.
So, can be simultaneously, efficiently the waste liquid that contains TMAH and ammonia is become harmless N 2, CO 2, H 2O.
Again, as mentioned above, above-mentioned well heater 83 can be used well-known methods such as electrically heated, roasting kiln, the fuel of above-mentioned roasting kiln can be used kerosene, liquefied gas (LPG), piped gas, contains the waste liquid of Virahol and the solvent slop discharges such as matting of semiconductor device manufacturing works (often from) in addition and uses as the fuel of above-mentioned roasting kiln.
Embodiment 7
Fig. 7 is the mode chart of the refining plant of relevant embodiments of the invention 7.With the same component part of Fig. 4 with same symbolic representation, to avoid repeat specification.
In the embodiment of the invention 7, innoxious gas (gas after the processing) vent pipe 85 of deriving from hydrogen-catalyst reactor 18 has 2 branches, a branch line 86a is connected with heat exchanger 87 with gasification, and another branch line 88a is connected with heat exchanger 89 with air heating.
Above-mentioned gasification utilizes the ammoniated gas in the heat exchange heated air vent pipe with being connected with the gas outlet pipe road 64a that derives from gas stripping column 26 on the heat exchanger 87.With the downstream side of heat exchanger 87 well heater 58 is installed in gasification, can be heated to the above-mentioned concentrated solution necessary temperature (200-600 ℃) that gasifies.Pipe arrangement 64b through well heater 58 links to each other with gasifier 16, and it keeps heat can be used in the gasification of above-mentioned concentrated solution.
On the other hand, above-mentioned air heating is with being connected with the air leading-in conduit 51a that is used for importing to gas stripping column 26 air on the heat exchanger 89.Utilize heat exchange, can heat the air in the air leading-in conduit.Be admitted to gas stripping column 26 with the air that heat exchanger 89 heats by air leading-in conduit 51b by this air heating, the gas that is used for ammonia is carried.
Innoxious gas behind over-heat- exchanger 87,89 mixes in the pipeline 52 of interflow by vent pipe 86b, 88b, is disposed in the atmosphere.
As mentioned above, because the innoxious gas temperature of discharging from above-mentioned hydrogen-catalyst reactor 18 is higher,, then can effectively utilize heat if heat is reclaimed, utilizes by above-mentioned heat exchanger 87,89.And as above-mentioned well heater 58, well-known method heating such as available electrically heated, roasting kiln, the fuel of above-mentioned roasting kiln can be used kerosene, liquefied gas (LPG), piped gas, contains the waste liquid and the solvent slop (normal discharges such as matting from semiconductor device manufacturing works) of Virahol in addition.
In present embodiment 7, also as above-mentioned, can be simultaneously, efficiently the wastewater treatment that contains TMAH and ammonia is become harmless N 2, CO 2, H 2O, its thermo-efficiency height.
In addition, in the foregoing description 4-7, be that purifying treatment with the waste water that contains ammonia and TMAH is an example, but be not limited to above-mentioned waste water, also can purifying treatment contain the gasifiable organic compound beyond the TMAH and the waste water of ammonia, for example, but purifying treatment contains the waste water of organic compounds containing nitrogens such as 2-pyrrolidone and ammonia.
When relating to the maintenance heat that utilizes the innoxious gas that hydrogen-catalyst reactor 18 discharges, be to go out in advance with the gas handling among the foregoing description 6-7 that the type treatment process is an example, but in concentrating in advance the type treatment process, equally also can utilize the maintenance heat again.
Experiment 1
Below, be treated to example so that carry out draining with the treatment unit of the foregoing description 1.Make as the waste water of process object and to consist of: contain the waste water [A] of TMAH, its concentration is 3000mg/L; Ammoniated waste water waste water [B], its concentration are 2500mg/L.
At first, add alkali (NaOH) to waste water [B] in PH adjustment groove 24, regulate pH and reach 11.5, this waste water [B] that has added alkali injects from the top of gas stripping column 26 with the speed of 800L/hr.At this moment, from the bottom of gas stripping column 26, with 850m 3The speed of (routine)/hr provides high temperature air (150 ℃).Discharge not ammoniated waste water from the bottom of gas stripping column 26.Again, the ammoniated gas of discharging from the top of gas stripping column 26 imports well heater 35, after intensification is heated to 500 ℃, imports gasifier 16.
On the other hand, waste water [A] is imported thickener 14, make its concentration reach about 6%, be sprayed in the above-mentioned gasifier 16, liquid is all gasified with the speed of 40L/hr.In this gasification process, TMAH is thermal decomposited gasification and is methyl alcohol and Trimethylamine 99.
The gas that contains ammonia, methyl alcohol, Trimethylamine 99 of discharging from gasifier 16 is imported into the hydrogen-catalyst reactor 18.The catalysis temperature in of reactor 18 is 330 ℃.Be pre-charged with catalyzer 250L described later in the reactor 18 again.
The analytical results of the purified gas of discharging from reactor 18 is as follows:
Trimethylamine 99: below the detection limit
Methyl alcohol: below the detection limit
Ammonia: below the detection limit
Oxynitride: 15ppm
Carbonic acid gas: 2600ppm
Carbon monoxide: below the detection limit
The above-mentioned catalyzer of filling in the reactor 18 disposes with following method.Promptly in the ammoniacal liquor of 700 liter 10% (quality), add the silicon sol of 35.5kg20% (quality), after mixing was stirred, in titanium sulfate, 300 liters of aqueous sulfuric acids were stirred on the limit, and (TiO slowly drips on the limit 2The 152g/ liter, H 2SO 40.55kg/ rise).The resulting gel of slaking, after the filtration washing, drying is 10 hours under 150 ℃, then 500 ℃ of following roastings 6 hours.It is TiO that the powder that obtains is formed 2: SiO 2=4: 1 (mol ratio), BET specific surface area are 200m 2/ g.In this 20kg powder, add the 15% monoethanolamine aqueous solution 12kg that contains ammonium meta-vanadate 2.00kg and ammonium metawolframate 0.77kg.Add starch again as shaping assistant, grind mix after, with extrusion shaping machine be configured as that outside dimension 800mm is square, opening 2.8mm, thick 0.5mm, long 450mm cellular.Dry under 80 ℃ it, then in 450 ℃ air, burnt till 5 hours.The composition of this honeycomb formed article is Ti-Si composite oxides: V2O5: WO 3=90: 7: 3 (weight ratio).After this formed body soaked in the platinum nitrate aqueous solution, 150 ℃ dry 3 hours down, in 450 ℃ air, burnt till 3 hours.The composition of the catalyzer that obtains is: Ti-Si composite oxides: V 2O 5: WO 3: Pb=89.1: 6.9: 3: 1 (weight ratio), the BET specific surface area is 120m 2/ g, pore volume is 0.45cc/g.
Experiment 2
Below, use treatment unit of the foregoing description 4 and treatment process to carry out wastewater treatment for example.The waste water composition of process object is: contain the waste water [A] of TMAH, concentration is 3000mg/L; Ammoniated waste water, concentration are 2500mg/L.
At first, waste water is injected from the top of gas stripping column 26 with the speed of 800L/hr.At this moment, from the bottom of gas stripping column 26 with 850m 3The speed of (routine)/hr imports high temperature air (150 ℃).Then, the waste water that contains TMAH simmer down to concentration in thickener 66 that the bottom of gas stripping column 26 is discharged is 6% TMAH.
On the other hand, via air leading-in conduit 68, to the ammoniated gas of discharging from the top of gas stripping column 26 with air 200Nm 3The speed of/h adds air, imports heating part 6.With fuel feed heating part 65, be warmed up to 500 ℃ after, this high-temperature gas is imported gasifier 16.Be sprayed in the above-mentioned gasifier 16 in the speed of above-mentioned thickener 66 spissated TMAH concentrated solutions, make it whole gasifications with 40L/hr.In gasification process, TMAH is thermal decomposited into Trimethylamine 99 and methyl alcohol.
The gas that contains ammonia, Trimethylamine 99, methyl alcohol of discharging from gasifier 16 is imported into hydrogen-catalyst reactor 18.The catalysis temperature in of hydrogen-catalyst reactor 18 is 330 ℃.Be filled with following catalyzer 250L in the hydrogen-catalyst reactor 18 again.
The analytical results of the purified gas of discharging from reactor 18 is as follows:
Trimethylamine 99: below the detection limit
Methyl alcohol: below the detection limit
Ammonia: below the detection limit
Oxynitride: 15ppm
Carbonic acid gas: 2600ppm
Carbon monoxide: below the detection limit
Be filled with catalyzer with above-mentioned experiment 1 the same configuration in the hydrogen-catalyst reactor 18 again.
The invention effect
According to method of wastewater treatment of the present invention and treatment unit, can be different types of waste water, or contain the waste water that annoying handlings such as gasifiable organic compound such as TMAH and ammonia go out compound and be processed into harmless N simultaneously 2, CO 2, H 2O etc.Compare with the existing situation of handling above-mentioned gasifiable organic compound and above-mentioned ammonia etc. respectively, device of the present invention is simple, the efficient height, and facility investment and operating cost reduce.

Claims (14)

1 one kinds of method of wastewater treatment, described method of wastewater treatment is a kind of method of wastewater treatment that can handle two or more waste water simultaneously, the a kind of of above-mentioned waste water is the waste water A that contains gasifiable organic compound, the another kind of above-mentioned waste water is to contain the waste water B that can carry out the compound that gas carries with gas, it is characterized in that aforesaid method comprises:
The gasification process of the above-mentioned waste water A that gasifies;
From above-mentioned waste water B, gas is put on and is stated and can put forward operation with the gas that gas carries out the compound that gas carries;
The gas that will be obtained by above-mentioned gasification process and carry the gas that operation obtains by above-mentioned gas and mix carries out the decomposition process of disaggregating treatment through catalyzer.
2 method of wastewater treatment as claimed in claim 1 is characterized in that, the enrichment process that concentrates described waste water A was set before above-mentioned gasification process.
3 one kinds of method of wastewater treatment, described method of wastewater treatment are a kind of method of wastewater treatment that contains gasifiable organic compound and can carry out the compound that gas carries with gas, it is characterized in that aforesaid method comprises:
Put on from liquid phase gas and to state and to put forward operation with the gas that gas carries out the compound that gas carries;
Concentrate the enrichment process of above-mentioned gasifiable organic compound;
The gasification process of the concentrated solution that the gasification enrichment process obtains;
To carry the decomposition process that gas that operation obtains decomposes under the situation that catalyzer exists at gas that gasification process obtains with at above-mentioned gas.
4 method of wastewater treatment as claimed in claim 3 is characterized in that, carried out described gas earlier and put forward operation before above-mentioned enrichment process, the attached described enrichment process of liquid phase after gas is carried.
5 method of wastewater treatment as claimed in claim 3, it is characterized in that above-mentioned enrichment process adopts heat energy, carries out described enrichment process before above-mentioned gas is put forward operation earlier, will be by the attached condensation operation of the gas phase that enrichment process obtains, the described gas that resulting water of condensation is attached is put forward operation.
6 each described method of wastewater treatment as claim 1-5 is characterized in that, the heat that is used to the gas maintenance after the processing of above-mentioned decomposition process is as the required heat of above-mentioned gasification process gasification.
7 as claim 1 or 3 described method of wastewater treatment, it is characterized in that, will carry the gas that operation obtains via above-mentioned gas and propose the attached harmless treatment of back waste water.
8 as claim 1 or 3 described method of wastewater treatment, it is characterized in that, above-mentioned to carry out the compound that gas carries with gas be ammonia, and above-mentioned gasifiable organic compound is a tetraalkylphosphoniuhydroxide hydroxide ammonia.
9 one kinds of wastewater treatment equipments, described wastewater treatment equipment is a kind of wastewater treatment equipment that can handle two or more waste water simultaneously, the a kind of of above-mentioned waste water is the waste water A that contains gasifiable organic compound, the another kind of above-mentioned waste water is to contain the waste water B that can carry out the compound that gas carries with gas, it is characterized in that said apparatus comprises:
The gasification portion of the above-mentioned waste water A that gasifies;
Gas is put on and is stated and can carry portion with the gas that gas carries out the compound that gas carries from above-mentioned waste water B;
The gas that will obtain by above-mentioned gasification portion, and carry the gas that obtains by above-mentioned gas and mix, carry out the decomposition portion of disaggregating treatment through catalyzer.
10 wastewater treatment equipments as claimed in claim 9 is characterized in that, before waste water being imported described gasification portion, the concentrated portion that concentrates described waste water A are set.
11 1 kinds of wastewater treatment equipments, described wastewater treatment equipment are a kind of to containing gasifiable organic compound and can carrying out the device that the waste water of the compound that gas carries is handled with gas, it is characterized in that said apparatus comprises:
Put on to state from liquid phase gas and can carry out gas with gas and carry the gas of compound and carry portion;
Above-mentioned gasifiable organic compound is carried out spissated concentrated portion;
To the gasification portion of gasifying from the concentrated solution that concentrates portion's discharge;
Will be from gasification portion expellant gas and the decomposition portion that under the situation that catalyzer exists, decomposes at the gas that the above-mentioned gas portion of carrying obtains.
12 wastewater treatment equipments as claimed in claim 11 is characterized in that, described device comprises:
Above-mentioned waste water is imported the pipeline that above-mentioned gas is carried portion, and
To import the pipeline of described concentrated portion from the liquid phase that the gas portion of carrying discharges.
13 wastewater treatment equipments as claimed in claim 11 is characterized in that, described device comprises:
Above-mentioned waste water is imported the pipeline of above-mentioned concentrated portion,
Heat the heating unit of above-mentioned concentrated portion,
The gas phase that the portion that concentrates is discharged imports the pipeline of condensation part, and
The condensed water that the condensation part is discharged imports the pipeline that gas is carried portion.
14 each described wastewater treatment equipments as claim 9-13 is characterized in that, the heat that the gas after the above-mentioned decomposition portion that is used to hang oneself handles keeps is as the required heat of above-mentioned gasification portion's gasification.
CNB021027870A 2001-02-02 2002-02-01 Waste water treatment process and treatment appts. Expired - Fee Related CN1176031C (en)

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